Polyimides are among the most important high-performance glassy polymeric materials that exhibit exceptional thermal, chemical and mechanical properties. Consequently, they have been practically applied in a wide range of fields such as aerospace technology, electronics industry, and can be used for high temperature adhesion, membranes for separation, composite materials, and the like. Currently, the most important commercialized polyimides in practical usages are Kapton, Upilex, Matrimid, P84, and Ultem. However, these polyimides exhibit poor processability due to their high melting temperature and limited solubility in organic solvents, resulting in great restriction in practical usage. Microporous polyimides, formed by condensation of the dianhydrides and diamines containing site of contortion, have been developed to overcome these deficiencies. However, microporous polyimides are challenging to synthesize due, at least in part, to limitations of suitable monomers, especially those dianhydrides.